Process for synthetically preparing ammonia and other compounds containing nitrogen and hydrogen.



UNITED STATES PATENT OFFICE.

FAUSTIN HLAVATI, F VIENNA, AUSTRIA-HUNGARY.

rnoonss ron SYNTHETIGALLY PREPARING AMMONIA AN'I'J OTHER oonroUNfis 1 CONTAINING NITROGEN AND HYDROGEN.

Nb Drawing.

' specification f Letters Patent. Application filed February 13, 1913. Serial No. 748,223.

5 invented new and useful Improvements in.

' the ratio of their atomic weights, this mix Processes for Synthetically Preparing'Ammonia and other Compounds Containing Nitrogen and Hydrogen, of which the following is a specification. I

This invention relates to a process for the s nthesis of ammonia (NH,), diamid (N HZ), hydroxylamin (NI-LOH) "and other compounds containing nitrogen and hydrogen from their elements, which isequally applicable to a pure mixture of 3 parts by volume of pure hydrogen and 1 part by volume of pure nitrogen, or to combustion gases of any furnace plant, or producerand water-gas in proper proportions as above mentioned, from which gases the carbonic oxid has been separated by cuprous chlorid' ((111,01 solution. The small quantities of carbon dioxid, methane, oxygen and water which are containedin gas mixtures consisting of 3 parts by volume of hydrogen mixed with 1 part by volume of nitrogen, do not prevent the production of nitrogen hydrogen compounds in this process, if these gas mixtures after having been ionized by electrical means and thereafter sufiiciently cooled are conducted over a suitably insulated contact substance consisting of platinum and titanium or palladium and titanium, or of a mixture of a metal or metals belonging to the platinum group with titanium, intimately mixed together, preferably inture being, in a finely distributed condition,

precipitated upon in different substances as for instance tufi', asbestos, &c., upon which it is present in the form of firmly adhering metallic pairs. I

If apparatus of any construction is at. hand, which is capable of withstanding high internal pressure and which for instance contains several tubes or chambers the same are filled with the contact material, which as above described consists of the finely dis-.

tributed metals precipitated upon and firmly adhering to an indifferent substance. Through these filled tubes or chambers is conducted a gas mixture ionized as above mentioned by means of electrical influence: This gas mixture however being heated up to about 1000 C. by electrical discharges,

means of the supply of fresh hot gases, the

absorbed gases are forced to escape from the metallic pairs in the nascent state and to combine to form ammonia (11.8 calories being given off from each grain-molecule of ammonia produced) and the temperature in the apparatus rises gradually to such an extent, that the absorption of the gases is prevented andfurther ammonia synthesis ceases. To remove this drawback the gases have to be forced into the'chambers under a pressure of at least one atmosphere above Patented Nov. 25, 1913.

normal and at the same time the'cham'bers have to be gradually cooled by sprinkling with cold water to such an extent that the temperature in the last chamber sinks to about 6070 C. As during this process various metallic bases, containing platinum formed in consequence of the oxygen and water contained in the gases as for instance Pt(NH,),(OH) and Pt(NH ),,(OH) (the same as is the case with other metals of the platinum group) the gases must be quickly sucked from the apparatus and passedthrough acid or water to retain the nitrogen hydrogen compounds. The'residual gases escaping from the water or acid are mixed withv fresh gas mixture, again ionized and conducted in reverse direction through the contact masses, in order to force the combined ammonia to be given off from the catalysts'on account oftheir high temperature. .If two or more, sets of a paratus of such construction are at hand through which the ionized gases are always passed alternately in reverse direction while maintain- .ing the requisite temperature, a continuous production of ammonia can be insured.

To avoid the necessity of entirely or at least partly ionizing the gas mixture by electrical discharges, as certain operators would be without the necessary water power for economically producing the requisite electric energy, the process offers to such tainable.

operators the possibility of cheaply producing ammonia and other nitrogen and hydrogen compounds by means of X-rays (emanation) from pitch blend, mesothorium, or from other radio-active substances easily ob- The above mentioned 'gas mixture of 3 parts by 'volumeof hydrogen and I clear, the following specific example is given,

but the claims are not to be construed as limited to this particular. example. In carrying out my process, I may obtain the nitrogen, by passing the products of combustion of any suitable furnace, such as a steam boiler furnace, which gases contain nitrogen, carbon dioxid, carbon 'monoxid, together with traces of methane and oxygen, through milk of lime or othersuitable absorbent to absorb the carbon dioxid, and then through through a vessel in which means are aran alkaline solution of cuprous chlorid, to 1 absorb carbon monoxid I then add to this purified gas, a sufiicient amount of a gas consisting essentially of hydrogen, to produce a gas mixture containing one part -by volume of nitrogen to three parts by volume of hydrogen. This mixture is conducted ranged for producing a so called electric brush discharge, whereby the nitrogen and hydrogen molecules are ionized. The ionized. gas mixture is then introduced into an apparatus consisting of a pluralit of tubeshaped chambers, preferably ma e of copper and filled with suitable catalytic substances.- As a catalyst I'preferably employ a mixture of platinum and titanium precipie tated in a finely divided condition on a suitable porous substance as for instance porous burnt clay, .or asbestos. To produce the catalytic material, I dissolve platinum chlorid and titanium tetrachlorid in ver concentrated hydrochloric acid, preferably in about the ratio of the atomic weights of the said metals, that is to say, the final mass should contain 195 parts by weight of platinum and 48 parts of titanium. I then take smallrpiecesof rous cla or its equivalent,-

referably in t e form 0 small balls and I lmpregnate them with the said hydrochloric acid solution of platinum and titanium chlorids.. The mass is dried and the metallic chlorids are then reduced by heating the mass in a current of hydrogen gas. Thereafter the same may be heated in a current of nitrogen or ammonia gas to a temperature of eon-950 0. After being thus treated, the

catalyst is filled into said tubes and the above mentioned mixture of nitrogen and hydrogen is conducted through the said tubes containing the contact mass, 'atleast some of said tubes being at a temperature of about 200- to 250 0.. .Care should be taken that the temperature does. not attain 300 at any time in the coolest contact mass. After having passed the catalytic apparatus, the gas mixture, which then contains a certain amount of ammonia (and, which in the presence of water or free oxygen will also contain hydroxylamin) is treated with an acid solution for instancesulfuric acid to absorb the ammonia or other volatile bases. The

gas mixture having this been freed from nitrogen compounds may be reused by conducting it again through the catalytic apparatus.

It may occur that platinum-ammonia compounds such as Pt(l lH,,) (OH) or Pt (NH ,(OI-I), are formed in the catalytic mass especially in the last chambers, where the temperature will usually be much lower than in the first chambers. To decompose the said platinum-ammonia compounds and to regenerate the catalystthe gas current is reversed after some time in the catalytic apparatus and the chambers are heated to 300 C. or over, or the pressure may be reduced for some time, while at a temperature of 200 to 250 6..

The term a metal of the platinum group as used in the appended claims is intended to cover a single metal or a mixture or alloy of two or more of such metals.

1. The herein described process of synthetically producing compotmds containing nitrogen and hydrogen, which process consists in. ionizing a gas mixture containing the said elements and passing the said mixture over a catalyst containing a metal of the platinum group and titanium.

2. The herein described Process of synthetically producing compounds containing nitro en and hydrogen, which process con sists 1n ionizing by electrical discharges a gas mixture containing the said elements and passing the said mixture over a catalyst containing a metal of the platinum ,grou

and titanium in the ratio of the atomlcweights of the said metals.

3. The herein describedprocess of synthetically producing compounds containing then raising the temperature to expel the said absorbed elements from the absorbing metal of the platinum grou p and titanium,-

metals ina chemically active condition, to and reversing the direction of the flow of cause said elements to combine. said gas mixture at intervals. 4:. The herein described process of syn- In testimony whereof I aflix my signature 5 thetically producing compounds containing in presence of two witnesses.

nitrogen and hydrogen, which process con- F AUSTIN HLAVAT'I sists in ionizing by electrical discharges a gas mixture containing the said element-s Witnesses:

and passing the said mixture over a plural- HENRY HAsPER, 10 ity of masses of a catalytic body including a WOLDEMAR 'HAUPT. 

